Production of Gasoline Components from Synthesis GasChE 397 Senior DesignGroup Alpha

Ayesha RizviBernard HsuJeff TyskaMohammed ShehadehYacoub Awwad

2011.02.15

Recap

H2

Block Flow Diagram

Methanol

Reactor

Wastewater

treatment

H2O, trace contaminants

CO

H2

MeOH DME

Reactor

Methanol to Gasoline Reactors

DME

H2O

MeOH

Distillation Columns

Heavy Gasoline

Light Gasoline

Storage

Crude Gasoline

Light Gas

Overall Flowsheet

Mass Balance Basis: 3307 Tons per Day Syn Gas

Syngas to Methanol

CO: 8611.72 lbmol/hrH2: 17223.45 lbmol/hr

CO: 141.09 lbmol/hrH2: 18.48 lbmol/hr

CO: 243.98 lbmol/hrH2: 594.88 lbmol/hr

Mass Balance Basis: 3307 Tons per Day Syn Gas

MeOH: 8226.65 lbmol/hr

DME reaction

MeOH: 8226.65 lbmol/hrMeOH: 2468.00 lbmol/hrDME and H2O: 2879.33 lbmol/hr

Mass Balance Basis: 3307 Tons per Day Syn Gas

Methanol to Gasoline

Effluent: 8226.65 lbmol/hr

After the MTG Reaction

Cooling Separator

End Refining

LPGPRG

Final Recycle

Material BalanceMethanol Reactor

Syn Gas: CO: 8612 lbmol/hr purge: CO: 244 lbmolH2: 17223 lbmol/hr H2: 594.9 lbmol

Recycle: CO: 12199 lbmol/hr product: CO: 141.1 lbmolH2: 29744 lbmol/hr H2: 18.48 lbmol

MeOH: 8227 lbmol2.207505519

In Out

Material BalanceDME Reactor

MeOH: 8227 lbmol/hr MeOH: 2468 lbmol/hrH2O: 0 lbmol/hr H2O: 2879 lbmol/hr

DME: 2879 lbmol/hr

2.207505519

In: Out:

Material BalanceComponent Profile

Component lbmol/hrH2 0C1 27.55832CO 0CO2 0C2 = 7.873805C2 8.818661C3 = 10.49841C3 162.3435iC4 142.1629C4 = 10.23595nC4 42.57285

Component lbmol/hrC5's 58.87856C6's 7.870113C7's 3.148045C8's 1.83636C9's 0.655843C10's 0.131169Benzene 9.610079Toluene 50.32388C8 AROM 74.84642C9 AROM 4.842082C10 AROM 1.832139C11 AROM 0.261734Methanol 0DME 0H20 2818.389

Total 3444.69lbmol/hr

Assumptions1. All H2 is taken away in the

light gas2. All CH4 is taken away in the

light gas3. All ethane is taken away in

the light gas4. 30% of the propane is taken

away in the light gas5. None of the butane is taken

away in the light6. All CO/CO2 is lost in the light

gas7. All water is immiscible with

the other components, leaves completely

8. Remaining components are in the second liquid phase

Continued above

Liquid Hydrocarbon Components C3 = 7.34888

C3 113.64iC4 142.163C4 = 10.2359nC4 42.5728C5's 58.8786C6's 7.87011C7's 3.14805C8's 1.83636C9's 0.65584C10's 0.13117Benzene 9.61008Toluene 50.3239C8 AROM 74.8464C9 AROM 4.84208C10 AROM 1.83214C11 AROM 0.26173Total 530.2

lbmol/hr

Material BalanceLPG Flowrates

lbmol/hr %

C1 0 0C2 = 0 0C2 0 0C3 = 7.348884 2.283334C3 113.6405 35.30864iC4 142.1629 44.1707C4 = 10.23595 3.180358nC4 42.57285 13.22759C5's 5.887856 1.829385Total 321.8489

lbmol/hr

Assumptions1. All of the remaining

propane goes out the vapor stream

2. All of the remaining butane goes out the vapor stream

3. 10% of the pentane goes out the vapor stream

4. The liquid component out the stripper is our final product

Material BalanceProduct Composition

C5's 52.9907C6's 7.870113C7's 3.148045C8's 1.83636C9's 0.655843C10's 0.131169Benzene 9.610079Toluene 50.32388C8 AROM 74.84642C9 AROM 4.842082C10 AROM 1.832139C11 AROM 0.261734

Total 208.3486lbmol/hr

Energy Balance

rxnMeOHMeOH

DMEH2O

Heat of formation: ΔHF= m DME,outΔHF(DME)+m MeOH,outΔHF(MeOH)+

mH2O,outΔHF(H2O)- mMeOH,inΔHF(MeOH) =

ΔHF=Σm*cp*(Tout-Tin)+Q Q:heat loss to surroundings Tin=590°F

-29.2 MM Btu/hr

Energy Balance

At heat loss of 3400 Btu Tout= 860°F Heat loss to surroundings negligible Reactor Sizing: PV=nRT V=315.6 Ft3

diameter d=8 Ft , height h=25 Ft considering the reactor as a cylinder Area=2*pi*(d/2)*h+2*pi*(r2 /4) =729 Ft2

Residence Time: 5 seconds for MeOH and Durene Reactor. 10 seconds for MTG Reactors.

Equipment Costs

Component Name Component Type Equipment Cost Total Direct Cost(USD) (USD)

DMEREACT DAT REACTOR 162000 450000FLASH-flash vessel DVT CYLINDER 143000 295100GASMEHX DHE FLOAT HEAD 25900 102000HCCOOLER DHE FLOAT HEAD 20200 98200HEATER DHE FLOAT HEAD 791300 1.21E+06HEATEX DHE FLOAT HEAD 47200 157800MEOHRXN DAT REACTOR 170000 4500003PHASESP-flash vessel DVT CYLINDER 47000 178200ACCMLTR-flash vessel DVT CYLINDER 42700 155700GASPROD1 DAT REACTOR 2.00E+06 6.00E+06GASPROD2 DAT REACTOR 2.00E+06 6.00E+06GASPROD3 DAT REACTOR 2.00E+06 6.00E+06HCSHEAT DHE FLOAT HEAD 16000 77100HEATER2 DHE FLOAT HEAD 14800 77700HEATER3 DHE FLOAT HEAD 14800 77700HEATER4 DHE FLOAT HEAD 14800 77700STRIPPER-cond DHE FIXED T S 15800 77300STRIPPER-cond acc DHT HORIZ DRUM 13100 69200STRIPPER-reb DRB U TUBE 13900 69900STRIPPER-reflux pump DCP CENTRIF 4200 30000STRIPPER-tower DTW TRAYED 89900 243700Catalyst Catalyst 10000000 10000000

Totals: 1.76E+07 3.19E+07USD USD

What affects the Gasoline Prices

Seasonal Switch in Gasoline blends

Crude Oil Cost

Taxes and Fees

Supply and Demand

Transportation and Distribution Cost

Pricing Gasoline

http://www.api.org/aboutoilgas/gasoline/upload/PumpPriceUpdate.pdf

Economics of Products Average gasoline price in the city of Chicago is

$3.29 per gallon

Nationwide the average is $3.13 per gallon

Our gasoline price with low olefin and low Durene is roughly about $ 2.63 per gallon

Product: $84.6 Million / year

LPG : $5.4 Million / year

Major Components of Gasoline

ComponentsTotal Percentage

Composition

n-Alkanes C5, C6, C7, C9, C10-C13 17.3%

Branched Alkanes C4, C5, C6, C7, C8, C9, C10-C13 32.0%

Cycloalkanes C6, C7, C85.0%

Olefins C6

1.8%

Aromatics Benzene, Toluene, Xylenes, Ethylbenzene, C3

– Benzenes, C4-Benzenes

30.5%

Properties of Gasoline Blends

Octane Number (MON/RON) ranges (83/96 – 90/102)

Reid Vapor Pressure (psi) ranges (5 - 12)

Final Boiling Point (°C) ranges (180 - 210)

Sulfur (ppm) ranges (10 - 50)

Mixtures of C5-C10 Hydrocarbons

Major Components of Gasoline

Newton County

MTG Process, IN

RefineryJoliet, IL

Refinery Whiting,

IN

Transporting to Refineries

Key supplier of refined petroleum products to the Midwest.

250,000 barrels of crude per day

Produces ~9 million gallons of gasoline, diesel fuel/day.

Joliet, IL

http://www.exxonmobil.com/Corporate/Files/joliet_brochure.pdf

Whiting, IN

405,000 barrels of raw crude oil/day

Produce 15 million gallons refining products.

Whiting Refinery Modernization Project

http://www.bp.com/sectiongenericarticle.do?categoryId=9030203&contentId=7055766#7205736

Transport of Gasoline Pipeline transport

Railroad transport

Gasoline truck transportation

Gasoline Blending Conversion process in petroleum refining

Fluid Catalytic Cracker (FCC)

Alkylate Catalytic Reforming

• Cracking hydrocarbons by vaporization

• breaking long chained high-boiling hydrocarbon molecules

• presence of a fluidized powdered catalyst

• Isobutane is alkylated with low molecular weight alkenes

• presence of a strong acid catalyst• sulfuric acid or

hydrofluoric acid

• Petroleum refinery naphtha • low octane

• high octane liquid products

Questions from Presentation 1

Catalysts: How long do they last? ZSM-5: Pressure and temp (305 psi,

350ºC) is 52 days Is gasoline >10% olefins?

No, our product is 3.73 wt% olefins. May change with other conditions

Durene High melting point 3-6% from literature 2% Limit

1% in our gasoline Blending Other Methods

End!

Questions From Last Presentation Removal of the water is desirable

because the catalyst may tend to become deactivated by the presence of the water vapor at the reaction temperatures employed, but this step is by no means essential

Sulfuric Acid Alkylation The Alkylation reaction combines

Isobutane with light Olefins primarily a mix of

Butylene and Propylene

in the presence of a strong acid catalyst, Sulfuric Acid

This process results in upgrading the gasoline blend to a high octane blending component.

Low Olefin Content (3.73 wt%)